EP0208346B1 - Procédé d'inversion par diffusion-transfert - Google Patents

Procédé d'inversion par diffusion-transfert Download PDF

Info

Publication number
EP0208346B1
EP0208346B1 EP86200716A EP86200716A EP0208346B1 EP 0208346 B1 EP0208346 B1 EP 0208346B1 EP 86200716 A EP86200716 A EP 86200716A EP 86200716 A EP86200716 A EP 86200716A EP 0208346 B1 EP0208346 B1 EP 0208346B1
Authority
EP
European Patent Office
Prior art keywords
image
light
layer
receiving layer
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP86200716A
Other languages
German (de)
English (en)
Other versions
EP0208346A2 (fr
EP0208346A3 (en
Inventor
René Maria De Keyzer
Robert Joseph Pollet
Leon Louis Vermeulen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert NV filed Critical Agfa Gevaert NV
Publication of EP0208346A2 publication Critical patent/EP0208346A2/fr
Publication of EP0208346A3 publication Critical patent/EP0208346A3/en
Application granted granted Critical
Publication of EP0208346B1 publication Critical patent/EP0208346B1/fr
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
    • G03C8/06—Silver salt diffusion transfer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/166—Toner containing

Definitions

  • the present invention relates to the photographic silver complex diffusion transfer reversal process (DTR-process), in particular to a method for improving the density and the tone of images, produced according to the DTR-process, in the image-receiving layer and also relates to a non-light-sensitive element or a processing solution comprising density- and/or tone-controlling compounds.
  • DTR-process photographic silver complex diffusion transfer reversal process
  • DTR-process The principles of the silver complex diffusion transfer reversal process, hereinafter called DTR-process, have been described e.g. in the U.S. Patent specification 2,352,014.
  • silver complexes are transferred by diffusion from a light-sensitive silver halide emulsion layer to an image-receiving layer, in which they are converted into a silver image by the action of development nuclei.
  • an image-wise exposed silver halide emulsion layer is developed by means of a processsing solution in the presence of (a) developing agent(s) and a silver ion complexing agent, also called silver halide solvent.
  • the silver halide in the exposed parts of a negative emulsion layer is developed to silver so that it cannot dissolve anymore and consequently cannot diffuse.
  • the silver halide in the unexposed parts of such negative emulsion layer is converted into soluble silver complexes by means of the silver halide solvent acting as a silver complexing agent.
  • the soluble silver complexes are transferred by diffusion to an adjacent image-receiving layer or an image-receiving layer brought into effective contact with the emulsion layer, to form in the presence of development nuclei that catalyze the reduction of transferred complexed silver ions a positive silver image or silver-containing image in the receiving layer.
  • a direct-positive silver halide emulsion layer When instead of a negative silver halide emulsion layer a direct-positive silver halide emulsion layer is used, the silver halide in the unexposed areas is developed and the silver halide in the exposed areas is transferred, as described hereinbefore, to form a negative silver image in the image-receiving layer.
  • effective contact is understood that dissolved silver salts can migrate by diffusion from the emulsion layer to the image-receiving layer, if desired, through an intermediate layer provided between this emulsion layer and this image-receiving layer. Whenever such intermediate layer is present, it must not impede the diffusion of the silver salts.
  • the density of the image formed in the image-receiving layer is sometimes unsatisfactory and the image tone may often be unpleasant e.g. brownish.
  • the U.S. Patent specification 3,017,270 describes the use of certain quaternary ammonium or ternary sulphonium compounds.
  • the JP Patent applications 57/22,236 and 57/78,536 the use of certain quaternary imidazolinium or tetrahydropyridinium compounds is described.
  • the U.S. Patent specification 4,310,613 the use of certain quaternary ammonium compounds is said to improve transmission density but likely to impair reflection density.
  • transmission density and "reflection density” as used herein are meant the diffuse transmission density and the diffuse reflection density respectively.
  • the diffuse transmission density is measured according to the requirements of American Standard PH 2.19 - 1959.
  • the diffuse reflection density is measured according to the requirements of American Standard PH 2.17 - 1958.
  • Reflection density is influenced by the speed of transfer image formation.
  • This speed of transfer image formation has an influence on the density build-up, on the speed of deposition of the image particles, on the concentration of the deposited image particles, on the depth of the deposition in the image-receiving layer, and on the form of the image particles.
  • the density build-up of the image in the image-receiving layer should be such that incident light is not scattered by metallic particles at its surface so as to avoid any bronzing effect and thus to ensure a substantially neutral tone.
  • scattering of incident light by image particles that lie deeper in the transfer image must occur if the transfer image is to have a high reflection density.
  • the physical development of silver should be homogeneous within the layer. At the same time, the development must not substantially decrease the transmission density.
  • the present invention provides a method of making an image according to the silver complex diffusion transfer reversal process, hereinafter called DTR-image, said method comprising image-wise exposing a photosensitive element comprising a photographic silver halide emulsion layer, developing the exposed emulsion layer with the aid of an alkaline processing solution in the presence of a silver halide solvent and causing silver complexes to diffuse from the emulsion layer into a non-light-sensitive image-receiving layer in the presence of development nuclei thereby to form a silver transfer image in that layer, said transfer image formation occurring in the presence of at least one s-triazolo-[1,5-a ]-pyrimidine, which influences the density and tone of said transfer image and is contained in said non-light-sensitive image-receiving layer or a non-light-sensitive hydrophilic colloid layer in water-permeable relationship therewith and/or in said alkaline processing solution, characterized in that said s-triazolo-[1,5-a
  • each of R1, R2, and R3, which may be the same or different, represents:
  • the present invention also provides a non-light-sensitive element comprising an image-receiving layer incorporating at least one 7-hydroxy-s-triazolo-[1,5-a ]-pyrimidine corresponding to the above general formula (I).
  • the present invention also provides a processing solution comprising at least one 7-hydroxy-s-triazolo-[1,5-a ]-pyrimidine corresponding to the above general formula (I).
  • At least one 7-hydroxy-s-triazolo-[1,5-a ]-pyrimidine corresponding to the above general formula (I) is incorporated in the element containing the non-light-sensitive image-receiving layer and/or is added to the processing solution.
  • the 7-hydroxy-s-triazolo-[1,5-a ]-pyrimidine compounds corresponding to the above general formula (I) can be prepared by techniques described by G. Fischer in Journal für Signalauforulsmaterialien 1 , 33-42 (1973). For instance, they can be prepared by condensation of a Beta-keto-ester or of a substituted Beta-ketoester with a 5-amino-1,2,4-triazole according to the following reaction scheme:
  • the compounds of the invention can be prepared very simply and very economically by the foregoing methods.
  • Compound 2 was prepared analogously to Compound 1 as described above, but from 3-methylthiomethyl-5-amino-1,2,4-triazole melting at 125°C and methyl acetoacetate in acetic acid. Yield: (42%). Melting point: 243°C.
  • Compound 9 was prepared analogously to Compound 1 as described above, but from 3-[2-(methylthio)-ethyl]-5-amino-1,2,4-triazole melting at about 110°C and methyl acetoacetate in acetic acid. Yield: (69%). Melting point: 222°C.
  • Compound 14 was prepared analogously to Compound 1 as described above, but from ethyl 4-methoxyacetoacetate boiling at 55-60°C/5 mm and prepared as described in Journal of Organic Chemistry , 2087 (1978). Yield: (75%). Melting point: about 265°C.
  • Compound 17 was prepared analogously to Compound 1 as described above, but from 4-(2-acetoxy-ethyl-thio)acetoacetic acid methyl ester boiling at 129-131°C/0.5 mm and prepared by alkylation of 2-acetoxy-ethanethiol with 4-chloro-acetoacetic acid methyl ester in a mixture of toluene and triethylamine. Yield: (85%). Melting point: about 120°C.
  • Compound 20 was prepared analogously to Compound 6 as described above, but from 4-[2-(ethylthio)-ethylthio]-acetoacetic acid ethyl ester boiling at 140-145°C/1 mm. Yield: (25%). Melting point: about 170°C.
  • Compound 24 was prepared analogously to Compound 1 as described above, but from 2-(acetoxy-ethylthio)-acetoacetic acid ethyl ester boiling at 108-110°C/0.5 mm and prepared by alkylation of 2-acetoxy-ethanethiol with 2-chloroacetoacetic acid ethyl ester in a mixture of toluene and triethylamine. Yield: (77%). Melting point: about 100°C.
  • Compound 25 was prepared analogously to Compound 18 as described above, but from Compound 24 as described above. Yield: (67%). Melting point: about 210°C.
  • the silver halide of the photographic silver halide emulsion of the photosensitive element used in accordance with the present invention preferably consists of at least 70 mole % of silver chloride, the remainder being preferably silver bromide.
  • the average silver halide grain size can e.g. be in the range of 200-300 nm.
  • a suitable coverage of silver halide expressed in g of silver nitrate per m2 is in the range of 1 to 5 g/m2.
  • the binder of the photographic silver halide emulsion layer preferably is gelatin. But instead of or together with gelatin, use can be made of one or more other natural and/or synthetic hydrophilic colloids e.g. albumin, casein, zein, polyvinyl alcohol, alginic acids or salts thereof, cellulose derivatives such as carboxymethyl cellulose, modified gelatin, etc.
  • the weight ratio of hydrophilic colloid to silver halide expressed as equivalent amount of silver nitrate in the silver halide emulsion layer(s) of the photosensitive element can e.g. be between 1:1 and 10:1.
  • the photosensitive element may contain in the photographic silver halide emulsion layer and/or in one or more layers in water-permeable relationship therewith any of the kinds of compounds customarily used in such layers for carrying out the DTR-process.
  • Such layers may comprise e.g. one or more developing agents, coating aids, stabilizing agents or fog-inhibiting agents e.g. as described in the GB Patent specification 1,007,020 filed March 6, 1963 by Agfa A.G., plasticizers, spectral sensitizing agents, development-influencing agents e.g.
  • polyoxyalkylene compounds, onium compounds, and thioether compounds as decribed in the US Patent specifications 2,938,792; 3,021,215; 3,038,805; 3,046,134; 4,013,471; 4,072,523; 4,072,523; 4,072,526; 4,292,400, and in the DE Patent specification 1,124,354, hardeners, spectral sensitizing agents, etc.
  • a suitable spectral sensitizing agent for use in the photographic silver halide emulsion layer is the compound corresponding to the following structural formula II:
  • the support of the photosensitive element used in accordance with the present invention can be of any of the support materials customarily employed in the art. They include paper, glass or film, e.g. cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film etc. as well as metal supports and metal supports laminated on both sides with paper. Paper supports coated on one or both sides with an Alpha-olefin polymer, e.g. polyethylene, are used preferably.
  • one side of its support can be coated with a polyethylene layer, whose specific density and/or thickness differ from those measured at the other side of the support. This compensation for the curling tendency can be improved by application of a hydrophilic colloid anti-curling layer optionally incorporating matting agents.
  • the emulsion-coated side of the photosensitive element can be provided with a top layer that contains water-permeable colloids.
  • a top layer that contains water-permeable colloids.
  • Such top layer will usually be free of gelatin. It must be of such nature that the diffusion is not inhibited or restrained. Such layer may act e.g. as an antistress layer.
  • Appropriate water-permeable binding agents for a layer coated on top of the photographic silver halide emulsion layer are e.g.
  • methyl cellulose the sodium salt of carboxymethyl cellulose, hydroxyethyl cellulose, hydroxyethyl starch, hydroxypropyl starch, sodium alginate, gum tragacanth, starch, polyvinyl alcohol, polyacrylic acid, polyacrylamide, polyvinyl pyrrolidone, polyoxyethylene, copoly(methylvinylether/maleic acid), etc.
  • the thickness of this layer depends on the nature of the colloid used.
  • Such layer if present, may be transferred at least partially to the image-receiving layer when the DTR-process comes to an end.
  • the silver halide emulsion of the photosensitive element used in accordance with the present invention is prepared in a known way by precipitation reaction of halides, e.g. ammonium halide, potassium, sodium, lithium, cadmium and strontium halide with silver salts, e.g. silver nitrate, in a hydrophilic protective binder, preferably gelatin.
  • halides e.g. ammonium halide, potassium, sodium, lithium, cadmium and strontium halide
  • silver salts e.g. silver nitrate
  • hydrophilic protective binder preferably gelatin.
  • developing agents are to be incorporated into the silver halide emulsion, they are added to the emulsion composition preferably after the chemical ripening stage following the washing of the emulsion.
  • the DTR-image can be formed in the image-receiving layer of a so-called single-support-element, also called "mono-sheet" element, which contains the photographic silver halide emulsion layer(s) and the image-receiving layer in water-permeable relationship, e.g. on top of each other, or the DTR-image can be formed in an image-receiving layer of a separate element, which is brought into contact with the photosensitive element preparatory to the silver complex diffusion.
  • a so-called single-support-element also called "mono-sheet” element, which contains the photographic silver halide emulsion layer(s) and the image-receiving layer in water-permeable relationship, e.g. on top of each other
  • the DTR-image can be formed in an image-receiving layer of a separate element, which is brought into contact with the photosensitive element preparatory to the silver complex diffusion.
  • this layer can be coated on an opaque or transparent support, which can be one of the supports described hereinbefore for the photosensitive element.
  • the mono-sheet element may consist of a layer pack comprising in the given order: a transparent film support e.g. a polyethylene terephthalate support, an image-receiving layer, a light-shielding pigment layer e.g. a layer containing titanium oxide, and a silver halide emulsion layer e.g. a negative-working silver halide emulsion layer, whereas the second element may comprise a transparent film support e.g.
  • the film support may carry an image-receiving layer on either side.
  • the mono-sheet element as well the second element may comprise other conventional layers e.g. subbing layers.
  • the image-receiving layer or a layer adjacent thereto and in water-permeable relationship therewith may contain one or more agents for promoting the reduction of the diffusing silver complexes into metallic silver, these agents being called development nuclei.
  • development nuclei have been described in the above-mentioned book by A. Rott and E. Weyde on pages 54-57.
  • Suitable development nuclei are e.g. colloidal silver, heavy metal sulphides e.g. cobalt sulphide, zinc sulphide, nickel sulphide, silver nickel sulphide.
  • a preferred type of development nuclei are silver nickel sulphide nuclei.
  • the development nuclei can also be incorporated into the processing liquid as described in GB Patent specification 1,001,558, filed April 13, 1962 by Gevaert Photo-Producten N.V.
  • the 7-hydroxy-s-triazolo-[1,5-a ]-pyrimidine compounds corresponding to the above general formula (I) can be incorporated into the non-light-sensitive image-receiving layer in amounts of 1 mg to 200 mg per m2. Preferably, they are incorporated into the non-light-sensitive image-receiving layer in amounts of 10 mg to 100 mg per m2. They can also be incorporated in equivalent operative amounts into a non-light-sensitive hydrophilic colloid layer that is in water-permeable relationship with the image-receiving layer.
  • non-light-sensitive element comprising an image-receiving layer
  • other substances can also be incorporated, which play a contributory part in the formation of the diffusion transfer images.
  • Such substances include black-toning agents, e.g. those described in GB Patent specification 561,875, filed December 3, 1942 by Ilford Ltd. and in BE Patent specification 502,525 filed April 12, 1951 by Agfa A.G.
  • a preferred black-toning agent is 1-phenyl-5-mercaptotetrazole.
  • the image-receiving layer may consist of or comprise any of the binders mentioned hereinbefore for the silver halide, gelatin being the preferred binder for the image-receiving layer.
  • the non-light-sensitive element may in the image-receiving layer or in a hydrophilic colloid layer in water-permeable relationship therewith comprise a silver halide solvent, e.g. sodium thiosulphate in an amount of approximately 0.1 g to approximately 4 g per m2.
  • a silver halide solvent e.g. sodium thiosulphate in an amount of approximately 0.1 g to approximately 4 g per m2.
  • the non-light-sensitive element may in the image-receiving layer or in a hydrophilic colloid layer in water-permeable relationship therewith comprise colloidal silica.
  • the image-receiving layer may have been hardened to achieve enhanced mechanical strength.
  • Appropriate hardening agents for hardening the natural and/or synthetic hydrophilic colloid binding agents in the image-receiving layer include e.g. formaldehyde, glyoxal, mucochloric acid, and chrome alum.
  • Hardening can also be effected by incorporating a hardener precursor in the image-receiving layer, the hardening of the hydrophilic colloid therein being triggered by the treatment with the alkaline processing liquid.
  • a suitable hardening agent is a triazine compound having the following structural formula V:
  • Suitable hardening agents for hardening the hydrophilic colloid binding agents in the image-receiving layer are vinylsulphonyl hardeners such as those described hereinbefore for the hardening of photographic hydrophilic colloid silver halide emulsions.
  • the image-receiving layer may also comprise plasticizers, optical brighteners, and substances improving its adherence to the support.
  • a suitable plasticizing binding agent includes repeating units x, y and z as represented in the following general formula VI:
  • a suitable optical brightening agent has the following structural formula VII:
  • epoxysilane compounds e.g. a compound having the following structural formula VIII:
  • an image-receiving layer to a film or paper support can be improved considerably by the presence in such image-receiving layer of a combination of colloidal silica and an above-mentioned epoxysilane.
  • a preferred combination is that of silica and the epoxysilane corresponding to formula VIII. This specific combination is called SiO2/epoxysilane hereinafter.
  • the adherence can also be improved with a dihydroxybenzene e.g. resorcinol and/or with succinimide.
  • the adherence can be further improved by combining colloidal silica, an epoxysilane, a dihydroxybenzene, and succinimide in the image-receiving layer.
  • colloidal silica SiO2
  • epoxysilane compounds e.g. the compound having the above structural formula VIII
  • a very interesting non-diffusing hardener composition for use in hydrophilic colloid covering layers or antistress layers of photographic silver halide emulsion layers.
  • the non-light-sensitive element may, in the image-receiving layer in operative contact with the developing nuclei, contain thioether compounds such as those described in GE Patent specification 1,124,354, in US Patent specifications 4,013,471 and 4,072,526, and in the published EU Patent application 0,026, 520.
  • the non-light-sensitive element comprising an image-receiving layer may be provided with printing matter, e.g. with any type of recognition data applied by any type of conventional printing process such as offset printing, intaglio printing, etc.
  • Preferred image-receiving layer compositions for use in accordance with the present invention comprise gelatin as binding agent, silver nickel sulphide development nuclei, and at least one 7-hydroxy-s-triazolo-[1,5-a ]-pyrimidine compound corresponding to the above general formula (I).
  • the processing solution for effecting the development of the exposed silver halide in the emulsion layer of the photosensitive element and the diffusion transfer of the silver complexes to the non-light-sensitive element is an alkaline solution.
  • the 7-hydroxy-s-triazolo-[1,5-a ]-pyrimidine compounds corresponds to the above general formula (I) can be added to the alkaline processing solution in amounts of 5 mg to 500 mg per litre. Preferably, they are added thereto in amounts of 10 mg to 100 mg per litre.
  • the developing agent or a mixture of developing agents can be incorporated into the alkaline processing solution and/or into the photosensitive element comprising a photographic silver halide emulsion layer and/or into the non-light-sensitive element comprising an image-receiving layer.
  • the developing agent(s) can be present in the silver halide emulsion layer but such agent(s) is (are) preferably present in a hydrophilic colloid layer in water-permeable relationship therewith, e.g. in an anti-halation layer adjacent to the silver halide emulsion layer of the photosensitive element.
  • the developing agent(s) When incorporated into the non-light-sensitive element comprising an image-receiving layer, the developing agent(s) can be present in the image-receiving layer or in a hydrophilic colloid layer in water-permeable relationship therewith.
  • the processing solution is merely an aqueous alkaline solution that initiates and activates the development.
  • Suitable developing agents for the exposed silver halide are e.g. hydroquinone-type and 1-phenyl-3-pyrazolidinone-type developing agents as well as p-monomethylaminophenol.
  • the silver halide solvent preferably sodium thiosulphate
  • the silver halide solvent can be incorporated into the non-light-sensitive element as mentioned above, but also integrally or partly into the alkaline processing solution.
  • the amount of silver halide solvent is in the range of e.g. 10 g/l to 50 g/l.
  • the alkaline processing solution usually contains alkaline substances such as tribasic phosphate, preserving agents e.g. sodium sulphite, thickening agents e.g. hydroxyethylcellulose and carboxymethylcellulose, fog-inhibiting agents such as potassium bromide, silver halide solvents e.g. sodium or ammonium thiosulphate, black-toning agents especially heterocyclic mercapto compounds e.g. 1-phenyl-5-mercaptotetrazole.
  • the pH of the processing solution is preferably in the range of 10 to 14.
  • alkaline substances for use in the alkaline processing solution combinations of sodium carbonate with sodium hydroxide and/or 2-methylamino-ethanol were found to be advantageous because of improved buffering action and retarded exhaustion of the processing solution.
  • the photographic elements for use in accordance with the present invention can be used in the form of roll film or sheet film or in the form of a filmpack e.g., for in-camera-processing.
  • the photographic elements used in accordance with the present invention can also be destined for the production of identification documents according to the DTR-process.
  • identification documents contain a photograph and/or identification data formed by diffusion transfer in an image-receiving layer on a polyethylene-covered paper support, which to exclude any forgery by alteration of the identification data and/or photograph, is laminated to a transparent protective cover sheet.
  • the transparent protective cover sheet usually is a thermoplastic resin sheet such as a polyester film sheet, e.g. a polyethylene terephtalate film sheet, which is coated with polyethylene at the side that is to be laminated against the image-receiving-layer carrying the identification data.
  • the dry emulsion layer was covered with the following top layer composition at a ratio of 1 l per 20 m2 and a temperature of 45°C: demineralized water 800 ml hydroxyethyl starch having a substitution degree of 0.27 hydroxyethyl groups 40 g ethanol 200 ml 1-phenyl-3-pyrazolidone 5 g hydroquinone 10 g 20% aqueous formaldehyde 10 ml
  • the resulting photosensitive element was image-wise exposed and then moistened, at the emulsion side only, with the following processing solution: demineralized water 1000 ml sodium phosphate 75 g anhydrous sodium sulphite 40 g anhydrous sodium thiosulphate 40 g
  • the moistened photosensitive element was brought in contact for 8 s with the image-receiving layer of a non-light-sensitive element, prepared by coating a paper support of 110 g/m2 on both sides with polyethylene at a ratio of 15 g/m2 per side, treating it with a corona discharge, and applying the following composition thereto at a ratio of 15 m2/l: demineralized water 750 ml gelatin 45 g silver sulphide/nickel sulphide development nuclei 7 g 2% aqueous solution of density/tone-controlling compound 7.5 ml saponin 10 g 20% aqueous formaldehyde 8.5 ml demineralized water to make 1000 ml
  • the transmission density (D TR ), the saturation density (D S ), and the reflection density (D RF ) of the positive print were measured.
  • Saturation density is the highest reflection density obtained in a DTR Image of a step wedge. It is found in the areas of lower amounts of transferred silver.
  • Compound A is a comparison compound, which has been described in US Patent specification 3,053,657 and corresponds to the formula: TABLE 2 Density- and tone-controlling compound (D TR ) (D S ) (D RF ) Concentration in mol per m2 Blank 3.21 1.74 1.55 - Compound A 3.07 1.75 1.58 76.5 x 10 ⁇ 6 Compound 2 3.14 1.95 1.75 71.4 x 10 ⁇ 6 Compound 9 2.83 1.77 1.62 66.9 x 10 ⁇ 6 Compound 15 3.06 1.94 1.78 76.5 x 10 ⁇ 6 Compound 21 2.91 1.87 1.70 58.5 x 10 ⁇ 6
  • the results listed in Table 2 show that the reflection density (D RF ) measured on the positive prints obtained with density- and tone-controlling compounds 2, 9, 15, and 21 according to the present invention is higher than that of the blank and of the comparison compound A.
  • the transmission densities (D TR ) are not substantially decreased.
  • the saturation density (D S ) of compounds 2, 9, 15, and 21 is higher than that of the blank and of the comparison compound A.
  • Photosensitive elements were exposed image-wise and moistened with a processing solution, as described in Example 1.
  • the moistened photosensitive elements were brought in contact for 8 s with non-light-sensitive elements prepared by coating polyethylene-covered paper support as described in Example 1 with the following composition at a ratio of 1 l per 23.5 m2: demineralized water 925 ml gelatin 47 g silver sulphide/nickel sulphide development nuclei 16.5 g saponin 2 g density- and tone-controlling compound 7 ⁇ 10 ⁇ 5 mol/m2
  • the results listed in Table 3 show that the reflection density (D RF ) measured on the positive prints obtained with density- and tone-controlling compounds 2, 6, 9, and 21 according to the present invention is higher than that of the blank and of the comparison compound A.
  • the transmission densities (D TR ) are not substantially decreased.
  • the saturation density (D S ) of compounds 2, 6, 9, and 21 is higher than that of the blank and of the comparison compound A.
  • the tone of the positive images obtained with the blank and with comparison compound A is brownish black, which suggests that light impinging thereon is scattered at the very surface of the images and thus gives rise to an unpleasant bronzing effect.
  • the tone of the positive images obtained with compounds 2, 6, 9, and 21 is a pleasant neutral black in consequence of the scattering of incident light on image particles that lie deeper into the positive image.
  • Photosensitive elements were exposed image-wise and moistened with a processing solution, as described in Example 1.
  • the moistened photosensitive elements were brought in contact for 30 s with non-light-sensitive elements prepared by coating polyethylene-covered paper support as described in Example 1 with the following composition at a ratio of 1 1 per 28.6 m2: gelatin 34.7 g silver sulphide/nickel sulphide development nuclei 22.9 g sodium isotetradecyl sulphate 2 g 20% aqueous formaldehyde 3.7 ml density- and tone-controlling compound 40 mg/m2 succinimide (*) demineralized water in an amount sufficient to make 1 1 (*) means that the amount is shown in Table 4 hereinafter.
  • the results listed in Table 4 show that the reflection density (D RF ) measured on the transfer images obtained with density- and tone-controlling compounds 6, 9, 15, and 21 according to the present invention is higher than that of the blank.
  • the supplemental presence of succinimide in the image-receiving layer or of aqueous dispersion of SiO2 or mixture of SiO2 and epoxysilane in the antistress layer gave an even higher increase of the reflection density (D RF ).
  • the transmission densities (D TR ) are not substantially decreased.
  • the tone of the transfer image obtained with the blank is red to reddish brown, which suggests that light impinging thereon is scattered at the very surface of the images and thus gives rise to an unpleasant toning effect.
  • the tone of the transfer images obtained with compounds 6, 9, 15, and 21 is a pleasant neutral grey in consequence of the scattering of incident light on image particles that lie deeper in the transfer image.

Claims (9)

  1. Procédé de préparation d'une image conformément au procédé d'inversion-transfert par diffusion de complexes d'argent (image DTR), ce procédé consistant à exposer en forme d'image un élément photosensible comprenant une couche photographique d'émulsion à l'halogénure d'argent, développer la couche d'émulsion exposée à l'aide d'une solution alcaline de traitement en présence d'un solvant pour l'halogénure d'argent et faire en sorte que les complexes d'argent diffusent depuis la couche d'émulsion dans une couche réceptrice d'image non photosensible en présence de germes de développement, pour former ainsi une image argentique de transfert dans cette couche, cette formation d'image de transfert ayant lieu en présence d'au moins une s-triazolo-[1,5-a]-pyrimidine qui influence la densité et le ton de l'image de transfert et qui est contenue dans la couche réceptrice d'image non photosensible ou dans une couche colloïdale hydrophile non photosensible en relation de perméabilité à l'eau avec cette dernière et/ou dans une solution alcaline de traitement, caractérisé en ce que la s-triazolo-[1,5-a]-pyrimidine répond à la formule générale (I) ci-après :
    Figure imgb0017
     dans laquelle :

    chacun des radicaux R¹, R² et R³, qui peuvent être identiques ou différents, représente :
    (a) - un atome d'hydrogène ;
    (b) - un groupe alkyle en C₁-C₈ ou
    (c) - un groupe Alk₁ - X - Alk₂ - Y - où
    Alk₁   représente un groupe alkyle en C₁-C₈, ou un groupe alkyle en C₁-C₈ substitué
    X   représente -O-ou -S-,
    Alk₂   représente un groupe alkylène en C₁-C₈, ou un groupe alkylène en C₁-C₈ substitué , et
    Y   représente une simple liaison, -O-, -S-, -CONH-, -SO₂NH- ou -NHCONH-,


    ou dans laquelle :

    chacun des radicaux R¹ et R² (identiques ou différents) représente un atome d'hydrogène ou un des groupes (b) ou (c) et R³ représente un groupe alkyl(en C₁-C₈)thio ou un groupe alkyl(en C₁-C₈)thio comprenant un groupe alkyle en C₁-C₈ substitué,

    au moins un des radicaux R¹, R² et R³ représentant, toutefois, autre chose qu'un atome d'hydrogène et autre chose qu'un groupe alkyle en C₁-C₈.
  2. Elément non photosensible destiné à être utilisé dans le procédé DTR, comprenant une couche réceptrice d'image non photosensible ou une couche colloïdale hydrophile non photosensible en relation de perméabilité à l'eau avec cette dernière, englobant au moins une 7-hydroxy-s-triazolo-[1,5-a]-pyrimidine, caractérisé en ce que la 7-hydroxy-s-triazolo-[1,5-a]-pyrimidine répond à la formule générale (I) présentée dans la revendication 1.
  3. Elément non photosensible selon la revendication 2, caractérisé en ce que la 7-hydroxy-s-triazolo-[1,5-a]-pyrimidine est présente dans la couche réceptrice d'image, à raison de 10 mg à 100 mg par m².
  4. Elément non photosensible selon la revendication 2 ou 3, caractérisé en ce que la couche réceptrice d'image et/ou la couche colloïdale hydrophile non photosensible en relation de perméabilité à l'eau avec cette dernière, comprend également au moins un des groupes comprenant la combinaison de silice colloïdale et d'un époxysilane, un dihydroxybenzène et du succinimide.
  5. Elément non photosensible selon la revendication 4, caractérisé en ce que la couche réceptrice d'image comprend du succinimide et en ce que la couche colloïdale hydrophile non photosensible en relation de perméabilité à l'eau avec la couche réceptrice d'image, comprend de la silice colloïdale et/ou la combinaison de silice colloïdale et d'un époxysilane.
  6. Elément non photosensible selon la revendication 4 ou 5, caractérisé en ce que l'époxysilane répond à la formule structurale VIII :
    Figure imgb0018
  7. Elément non photosensible selon l'une quelconque des revendications 2 ou 6, caractérisé en ce qu'il contient des germes de développement de sulfure d'argent-nickel.
  8. Solution de traitement destinée à être utilisée dans le procédé DTR, comprenant au moins une 7-hydroxy-s-triazolo-[1,5-a]-pyrimidine, caractérisée en ce que la 7-hydroxy-s-triazolo-[1,5-a]-pyrimidine répond à la formule générale (I) présentée dans la revendication 1.
  9. Solution de traitement selon la revendication 8, caractérisée en ce que la 7-hydroxy-s-triazolo-[1,5-a]-pyrimidine est présente dans la solution de traitement à raison de 10 mg à 100 mg/l.
EP86200716A 1985-06-11 1986-04-28 Procédé d'inversion par diffusion-transfert Expired EP0208346B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP85200915 1985-06-11
EP85200915 1985-06-11

Publications (3)

Publication Number Publication Date
EP0208346A2 EP0208346A2 (fr) 1987-01-14
EP0208346A3 EP0208346A3 (en) 1989-03-01
EP0208346B1 true EP0208346B1 (fr) 1991-11-21

Family

ID=8194027

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86200716A Expired EP0208346B1 (fr) 1985-06-11 1986-04-28 Procédé d'inversion par diffusion-transfert

Country Status (4)

Country Link
US (1) US4859565A (fr)
EP (1) EP0208346B1 (fr)
JP (1) JPH0658523B2 (fr)
DE (1) DE3682543D1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4892945A (en) * 1987-12-21 1990-01-09 Ciba-Geigy Corporation Isoindoline pigments containing at least one triazolopyrimidone radical
GB9025365D0 (en) * 1990-11-21 1991-01-02 Kodak Ltd Diffusion transfer receiver
US5292631A (en) * 1992-06-03 1994-03-08 Eastman Kodak Company Radiographic elements with improved covering power
US5314790A (en) * 1992-06-03 1994-05-24 Eastman Kodak Company Tone control of photographic silver images
US5292627A (en) * 1992-06-03 1994-03-08 Eastman Kodak Company Tone control of photographic images
EP0672943B1 (fr) * 1994-03-04 2000-01-12 Agfa-Gevaert N.V. Matériau pour l'enregistrement d'images à l'halogénure d'argent et procédé d'obtention d'une image selon le procédé de diffusion-transfert de sel d'argent
ATE484505T1 (de) * 2006-11-23 2010-10-15 Novartis Ag 5-sulfanylmethylä1,2,4ütriazolä1,5-aüpyrimidin- - olderivate als cxcr2-antagonisten
EP2025512B1 (fr) * 2007-08-14 2011-05-18 Agfa Graphics N.V. Procédé de fabrication d'une plaque d'impression lithographique

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2852375A (en) * 1956-09-28 1958-09-16 Eastman Kodak Co New tetrazaindene compounds and photographic emulsions containing them
DE1070029B (fr) * 1958-03-31 1959-11-26
US3053657A (en) * 1959-05-04 1962-09-11 Eastman Kodak Co Photographic silver halide diffusion transfer process
FR1308696A (fr) * 1961-09-27 1962-11-09 Procédé de préparation de s-triazolo [2, 3-a] pyrimidines substituées et nouveaux composés de ce type
US3799926A (en) * 1965-01-15 1974-03-26 Minnesota Mining & Mfg Certain s-triazolo(1,5-a)pyrimidine compounds and their preparation
US3600171A (en) * 1968-11-01 1971-08-17 Eastman Kodak Co Sulfonamides in diffusion transfer systems
US3706568A (en) * 1971-04-06 1972-12-19 Eastman Kodak Co Photographic diffusion transfer product and process
JPS5778536A (en) * 1980-11-04 1982-05-17 Mitsubishi Paper Mills Ltd Silver complex salt diffusion transfer image receptor
US4605609A (en) * 1983-09-09 1986-08-12 Mitsubishi Paper Mills, Ltd. Image receiving material with low calcium gelatin
EP0190375B1 (fr) * 1985-02-04 1989-04-19 Agfa-Gevaert N.V. Triazolopyrimidines substituées et leur utilisation pour matériau sensible à la lumière
GB8509381D0 (en) * 1985-04-12 1985-05-15 Ciba Geigy Ag Tetra-aza indene compounds

Also Published As

Publication number Publication date
EP0208346A2 (fr) 1987-01-14
DE3682543D1 (de) 1992-01-02
EP0208346A3 (en) 1989-03-01
US4859565A (en) 1989-08-22
JPS61284764A (ja) 1986-12-15
JPH0658523B2 (ja) 1994-08-03

Similar Documents

Publication Publication Date Title
US4563410A (en) Method for the preparation of a planographic printing plate using NiS containing nuclei
US3300306A (en) Process for the manufacture of printing plates
EP0218753B1 (fr) Elément récépteur pour le procédé d'inversion par diffusion-transfert de sels d'argent
EP0208346B1 (fr) Procédé d'inversion par diffusion-transfert
CA1124127A (fr) Materiel photographique pour reproduction continue des tons
EP0306561B1 (fr) Matériau récepteur d'image
EP0197202A1 (fr) Procédé photographique d'inversion par transfert par diffusion de complexes d'argent
GB2103382A (en) Improvement in or relating to a lithographic printing plate
EP0218752A1 (fr) Procédé d'inversion par diffusion-transfert de complexes d'argent
EP0496127B1 (fr) Plaque d'impression lithographique de type négatif basé sur le transfert de diffusion de sel d'argent
EP0449340B1 (fr) Stabilisateurs photographiques ayant un groupe développateur
EP0187879B1 (fr) Méthode et matériau pour la production d'images argentiques demi-ton au moyen du procédé par inversion de transfert de complexes d'argent par diffusion
US4945026A (en) Image receiving element for use in a silver salt diffusion transfer process
US4310613A (en) Liquid processing composition for silver complex diffusion transfer process
JPH04216545A (ja) 新規な写真安定剤
JPH0151176B2 (fr)
EP0491089B1 (fr) Méthode pour la préparation d'une image argentique
JPS6017440A (ja) 銀塩拡散転写法受像要素
EP0481132B1 (fr) Matériau de transfert de sels d'argent par diffusion négatif
JP2866207B2 (ja) 新規チオエーテル化合物及びそれを用いた平版印刷版用現像液
JP2895200B2 (ja) 平版印刷版用現像液
EP0489983A1 (fr) Cliché lithographique
JPH02201372A (ja) ネガ型平版印刷版の製造方法
JPH051935B2 (fr)
JP2000275857A (ja) 平版印刷版の処理方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE FR GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE DE FR GB

17P Request for examination filed

Effective date: 19890719

17Q First examination report despatched

Effective date: 19901119

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB

REF Corresponds to:

Ref document number: 3682543

Country of ref document: DE

Date of ref document: 19920102

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19960223

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19960224

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960226

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19960304

Year of fee payment: 11

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19970428

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19970430

BERE Be: lapsed

Owner name: AGFA-GEVAERT N.V.

Effective date: 19970430

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19970428

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19971231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST